Block copolymer

ABSTRACT

The present application provides the block copolymers and their application. The block copolymer has an excellent self assembling property and phase separation and various required functions can be freely applied thereto as necessary.

TECHNICAL FIELD

The present application relates to a block copolymer.

BACKGROUND

Block copolymers have molecular structures in which polymer subunitshaving chemically different structures from each other are linked bycovalent bonds. Block copolymers are capable of forming periodicallyaligned structure such as the sphere, the cylinder or the lamellathrough phase separations. Sizes of domains of the structures formed bythe self assemblies of block copolymers may be adjusted in a wide range,and various shapes of structures can be prepared. Therefore, they can beutilized in pattern-forming methods by lithography, various magneticrecording mediae or next generation nano devices such as metal dots,quantum dots or nano lines, high density magnetic storage mediae, andthe like.

DESCRIPTION Technical Object

The present application provides a block copolymer and its application.

Technical Solution

The term “alkyl group” as used herein may refer to, unless definedotherwise, an alkyl group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1to 4 carbon atoms. The alkyl group may have a linear, branched or cyclicstructure, and may be optionally substituted with at least onesubstituent.

The term “alkoxy group” as used herein may refer to, unless definedotherwise, an alkoxy group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or1 to 4 carbon atoms. The alkoxy group may have a linear, branched, orcyclic structure, and may be optionally substituted with at least onesubstituent.

The term “alkenyl or alkynyl group” as used herein may refer to, unlessdefined otherwise, an alkenyl or alkynyl group having 2 to 20, 2 to 16,2 to 12, 2 to 8, or 2 to 4 carbon atoms. The alkenyl or alkynyl groupmay have a linear, branched, or cyclic structure, and may be optionallysubstituted with at least one substituent.

The term “alkylene group” as used herein may refer to, unless definedotherwise, an alkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8 or1 to 4 carbon atoms. The alkylene group may have a linear, branched, orcyclic structure, and may be optionally substituted with at least onesubstituent.

The term “alkenylene or alkynylene group” as used herein may refer to,unless defined otherwise, an alkenylene or alkynylene group having 2 to20, 2 to 16, 2 to 12, 2 to 8 or 2 to 4 carbon atoms. The alkenylene oralkynylene group may have a linear, branched, or cyclic structure, andmay be optionally substituted with at least one substituent.

The term “aryl or arylene group” as used herein may be, unless definedotherwise, a monovalent or bivalent substituent derived from a compoundincluding one benzene ring structure or a structure, in which at leasttwo benzene rings are linked with sharing one or two carbon atoms or byan optional linker, or a derivative of the compound. The aryl or arylenegroup may be, unless defined otherwise, an aryl group having 6 to 30, 6to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms.

The term “aromatic structure” as used herein may refer to the aryl groupor the arylene group.

The term “alicyclic structure” as used herein may refer to, unlessdefined otherwise, a cyclic hydrocarbon structure that is not thearomatic cyclic structure. The alicyclic structure may be, unlessdefined otherwise, a structure having 3 to 30, 3 to 25, 3 to 21, 3 to 18or 3 to 13 carbon atoms.

The term “single bond” as used herein may refer to a case where there isno atom in a corresponding site. For example, a case where “B” is asingle bond in the structure represented by “A-B-C,” means that there isno atom in the “B” position and therefore the structure represented by“A-C” is formed by the “A” directly connecting to the “C.”

A substituent that may optionally substitute for the alkyl group, thealkenyl group, the alkynyl group, the alkylene group, the alkenylenegroup, the alkynylene group, the alkoxy group, the aryl group, thearylene group, a chain, the aromatic structure, and the like may behydroxyl group, halogen atom, carboxyl group, glycidyl group, acryloylgroup, methacryloyl group, acryloyloxy group, methacryloyloxy group,thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group,alkenylene group, alkynylene group, alkoxy group or aryl group, but isnot limited thereto.

In one embodiment, a monomer as represented by Formula 1 below that havea novel structure and that is capable of forming block copolymers may beprovided.

A monomer for forming a block copolymer represented by the Formula 1below:

In Formula 1, the R is hydrogen or an alkyl group and the X is thesingle bond, the oxygen atom, the sulfur atom, —S(═O)₂—, the carbonylgroup, the alkylene group, the alkenylene group, the alkynylene group,—C(═O)—X₁— or —X₁—C(═O)—. In the above, the X₁ may be the oxygen atom,the sulfur atom, —S(═O)₂—, the alkylene group, the alkenylene group orthe alkynylene group, and the Y may be a monovalent substituentincluding a cyclic structure to which a chain having 8 or morechain-forming atoms is linked.

In another embodiment, in the Formula 1, the X may be the single bond,the oxygen atom, the carbonyl group, —C(═O)—O— or —O—C(═O)—; or the Xmay be —C(═O)—O—, but is not limited thereto.

In Formula 1, the monovalent substituent Y includes a chain structureformed by at least 8 chain-forming atoms.

The term “chain-forming atoms” as used herein refers to atoms forming alinear structure of a certain chain. The chain may have a linear orbranched structure; however the number of the chain-forming atoms iscalculated only by the number of atoms forming the longest linear chain.Therefore, other atoms such as, in a case where the chain-forming atomis the carbon atom, the hydrogen atom that is linked to the carbon atomand the like are not calculated as the number of the chain-formingatoms. Further, in case of the branched chain, the number of thechain-forming atoms is the number of atoms forming the longest chain.For example, the chain is n-pentyl, all of the chain-forming atoms arecarbon atoms and the number thereof is 5. If the chain is2-methylpentyl, all of the chain-forming atoms are also carbon atoms andthe number thereof is 5. The chain-forming atoms may be the carbon, theoxygen, the sulfur or the nitrogen, and the like and appropriatechain-forming atoms may be the carbon, the oxygen or the nitrogen; orthe carbon or the oxygen. The number of the chain-forming atoms may be 8or more, 9 or more, 10 or more, 11 or more; or 12 or more. The number ofthe chain-forming atoms may be 30 or less, 25 or less, 20 or less or 16or less.

When the compound of the Formula 1 forms a block copolymer, the blockcopolymer may show an excellent self-assembly properties due to thepresence of the chain.

In one embodiment, the chain may be a linear hydrocarbon chain such as alinear alkyl group. In this case, the alkyl group may be an alkyl grouphaving 8 or more, 8 to 30, 8 to 25, 8 to 20 or 8 to 16 carbon atoms. Atleast one carbon atom of the alkyl group may be optionally substitutedwith the oxygen atom, and at least one hydrogen atom of the alkyl groupmay be optionally substituted with another substituent.

In Formula 1, the Y may include a cyclic structure. The chain may belinked to the cyclic structure. The self assembly properties of blockcopolymers formed by the compound may be further improved due to thecyclic structure. The cyclic structure may be the aromatic structure orthe alicyclic structure.

The chain may be directly linked to the cyclic structure or may belinked to the cyclic structure via a linker. As the linker, the oxygenatom, the sulfur atom, —NR₁—, —S(═O)₂—, the carbonyl group, the alkylenegroup, the alkenylene group, the alkynylene group, —C(═O)—X₁— or—X₁—C(═O)— may be illustrated. In the above, the R₁ may be the hydrogen,the alkyl group, the alkenyl group, the alkynyl group, the alkoxy groupor the aryl group and the X1 may be the single bond, the oxygen atom,the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, the alkenylenegroup or the alkynylene group and, in the above, the R₂ may be thehydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group. An appropriate linker may be the oxygenatom or the nitrogen atom. For example, the chain may be linked to thearomatic structure via the oxygen atom or the nitrogen atom. In thiscase, the linker may be the oxygen atom or the —NR₁—, where the R₁ maybe the hydrogen, the alkyl group, the alkenyl group, the alkynyl group,the alkoxy group or the aryl group.

In one embodiment, the Y of the Formula 1 may be represented by Formula2 below.

—P-Q-Z   [Formula 2]

In Formula 2, the P may be the arylene group, the Q may be the singlebond, the oxygen atom or —NR₃—, where the R₃ may be the hydrogen, thealkyl group, the alkenyl group, the alkynyl group, the alkoxy group orthe aryl group, and the Z may be the chain having at least 8chain-forming atoms. In case where the Y of the Formula 1 is thesubstituent of the Formula 2, the P of the Formula 2 may be directlylinked to the X of the Formula 1.

In Formula 2, an appropriate P may be an arylene group having 6 to 12carbon atoms such as the phenylene group, but is not limited thereto.

In Formula 2, an appropriate Q may be the oxygen atom or —NR₁—, wherethe R₁ may be the hydrogen, the alkyl group, the alkenyl group, thealkynyl group, the alkoxy group or the aryl group.

As an appropriate embodiment of the monomer of Formula 1, a monomer ofFormula 1, in which the R is the hydrogen atom or the alkyl group; orthe hydrogen atom or the alkyl group having 1 to 4 carbon atom(s), the Xis —C(═O)—O— and the Y is the substituent of Formula 2, in which the Pis the arylene having 6 to 12 carbon atoms or phenylene group, the Q isthe oxygen atom and the Z is the chain having 8 or more chain-formingatoms may be illustrated.

Therefore, as an appropriate embodiment, a monomer of Formula 3 belowmay be illustrated.

In Formula 3, the R is the hydrogen atom or the alkyl group having 1 to4 carbon atom(s), the X is —C(═O)—O—, the P is the arylene group having6 to 12 carbon atoms, Q is the oxygen atom, and Z is the above-describedchain having 8 or more chain-forming atoms.

Another embodiment of the present application relates to a method forpreparing a block copolymer comprising a step of forming a block bypolymerizing the monomer.

A specific method for preparing the block copolymer is not particularlylimited, as long as it comprises a step forming at least one block ofthe block copolymer by using the above-described monomer.

For example, the block copolymer may be prepared by a living radicalpolymerization (LRP) using the monomer. For example, there are methodssuch as the anionic polymerization, in which block copolymers aresynthesized in the presence of inorganic acid salts such as salts ofalkali metal or alkali earth metal by using organic rare earth metalcomplexes or organic alkali metal compounds as polymerizationinitiators; the anionic polymerization, in which block copolymers aresynthesized in the presence of organic aluminum compounds by usingorganic alkali metal compounds as polymerization initiators; theatom-transfer radical polymerization (ATRP) using an atom transferradical polymerizer as a polymerization controller; the activatorsregenerated by electron transfer (ATGET) ATRP performing polymerizationin the presence of an organic or inorganic reducing agent generatingelectrons using an atom transfer radical polymerizer as a polymerizationcontroller; the initiators for continuous activator regeneration (ICAR)ATRP; the reversible addition-ring opening chain transfer (RAFT)polymerization using an inorganic reducing agent reversibleaddition-ring opening chain transfer agent; and the a method using anorganic tellurium compound as an initiator, and an appropriate methodmay be selected among the above methods.

In one embodiment, the block copolymer may be prepared by a methodincluding polymerizing a material comprising monomers capable of formingthe block in the presence of radical initiators and living radicalpolymerization reagents by the living radical polymerization.

In the preparation of the block copolymer, a method for forming otherblock included in the block copolymer along with the block formed by theabove monomer is not particularly limited, and the other block may beformed by selecting appropriate monomers considering the kind of blocksto be formed.

The method for preparing the block copolymer may further includeprecipitating a polymerized product produced by the above-describedprocess in a non-solvent.

A kind of the radical initiators may be suitably selected inconsideration of polymerization efficiency without particularlimitation, and an azo compound such as azobisisobutyronitrile (AIBN) or2,2′-azobis-(2,4-dimethylvaleronitrile), or a peroxide compound such asbenzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP) may be used.

The LRP may be performed in a solvent such as methylenechloride,1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene,acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme,dimethylformamide, dimethylsulfoxide or dimethylacetamide.

As the non-solvent, for example, an alcohol such as methanol, ethanol,normal propanol or isopropanol, a glycol such as ethyleneglycol, or anether compound such as n-hexane, cyclohexane, n-heptane or petroleumether may be used without limitation.

Another embodiment of the present application relates to a blockcopolymer including a block (hereinafter, may be referred to as a firstblock) formed by using the monomer.

The block may be represented by, for example, Formula 4.

In the Formula 4, the R, X and Y may be the same as described regardingthe R, X and Y of the Formula 1, respectively.

Therefore, in Formula 4, the R may be hydrogen or an alkyl group having1 to 4 carbon atom(s), the X may be the single bond, the oxygen atom,the sulfur atom, —S(═O)₂—, the carbonyl group, the alkylene group, thealkenylene group, the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—,wherein the X₁ may be the oxygen atom, the sulfur atom, —S(═O)₂—, thealkylene group, the alkenylene group or the alkynylene group, and the Ymay be a monovalent substituent including a cyclic structure to which achain having 8 or more chain-forming atoms is linked. As for a specifictype of above each substituent, the above description may be applied inthe same manner

In one embodiment, the first block may be a block of the Formula 4, inwhich the R is the hydrogen or the alkyl group; or the hydrogen or thealkyl group having 1 to 4 carbon atom(s), the X is —C(═O)—O—, and the Yis the substituent represented by Formula 2. Such a block may bereferred to as a 1A block, but is not limited thereto. This block may berepresented by the Formula 5 below.

In Formula 5, the R may be the hydrogen atom or the alkyl group having 1to 4 carbon atom(s), the X may be the single bond, the oxygen atom,—C(═O)—O— or —O—C(═O)—, the P may be the arylene group, the Q may be theoxygen atom or —NR₃—, where the R₃ may be the hydrogen, the alkyl group,the alkenyl group, the alkynyl group, the alkoxy group or the arylgroup, the Z is the chain having 8 or more chain-forming atoms. Inanother embodiment, the Q of the Formula 5 may be the oxygen atom.

In another embodiment, the first block may be a block represented byFormula 6. Such a first block may be referred to as a 1B block herein.

In Formula 6, R₁ and R₂ may be each independently hydrogen or an alkylgroup having 1 to 4 carbon atom(s), the X may be the single bond, theoxygen atom, the sulfur atom, —S(═O)₂—, the carbonyl group, the alkylenegroup, the alkenylene group, the alkynylene group, —C(═O)—X₁— or—X₁—C(═O)—, in which the X₁ may be the single bond, the oxygen atom, thesulfur atom, —S(═O)₂—, the alkylene group, the alkenylene group or thealkynylene group, the T may be the single bond or the arylene group, theQ may be the single bond or the carbonyl group and the Y may be thechain having at least 8 chain-forming atoms.

In the 1B block of Formula 6, X may be the single bond, the oxygen atom,the carbonyl group, —C(═O)—O— or —O—C(═O)—.

As a particular embodiment of the chain Y in the 1B block, the abovedescription regarding Formula 1 may be applied thereto in a similarmanner.

In another embodiment, the first block may be a block represented by atleast one of the Formulas 4 to 6, in which the electronegativity of atleast one chain-forming atom of the chain having 8 or more chain-formingatoms is 3 or more. The electronegativity of the chain-forming atom maybe 3.7 or less in another embodiment. Herein, such a block may bereferred to as a 1C block. As the atom having the electronegativity of 3or more, the nitrogen atom or the oxygen atom may be illustrated, but isnot limited thereto.

Kinds of another block (hereinafter, may be referred to as a secondblock) included in the block copolymer along with the first block suchas the 1A, 1B or 1C block is not particularly limited.

For example, the second block may be polyvinylpyrrolidone block,polylactic acid block, polyvinylpyridine block, polystyrene block suchas polystyrene block or polytrimethylsilylstyrene, polyalkyleneoxideblock such as polyethyleneoxide block, or polyolefin block such aspolyethylene block or polyisoprene block or polybutadiene block. Such ablock used herein may be referred to as a 2A block.

In one embodiment, the second block included along with the first blocksuch as the 1A, 1B or 1C block in the block copolymer may be a blockincluding the aromatic structure comprising at least one halogen atom.

Such a second block may be, for example, represented by the Formula 7below and may be referred to as a 2B block.

In Formula 7, the B may be a monovalent substituent having an aromaticstructure including at least one halogen atom.

Such a second block may be effectively interacted with theabove-described first block such that the block copolymer can have anexcellent self assembling characteristic.

The aromatic structure of Formula 7 may be, for example, an aromaticstructure having 6 to 18 or 6 to 12 carbon atoms.

Further, the halogen atom included in Formula 7 may be, but is notlimited to, the fluorine atom or the chloride atom, and appropriatelythe fluorine atom.

In one embodiment, the B of Formula 7 may be a monovalent substituenthaving an aromatic structure having 6 to 12 carbon atoms, which issubstituted with 1 or more, 2 or more, 3 or more, 4 or more, or 5 ormore halogen atoms. The upper limit of the number of halogen atoms isnot particular limited, but there may be 10 or less, 9 or less, 8 orless, 7 or less, or 6 or less halogen atoms.

For example, the block represented by the Formula 7, which is the 2Bblock, may be represented by the Formula 8 below.

In Formula 8, the X₂ may be the single bond, the oxygen atom, the sulfuratom, —S(═O)₂—, the alkylene group, the alkenylene group, the alkynylenegroup, —C(═O)—X₁— or —X₁—C(═O)—, in which the X₁ is the single bond, theoxygen atom, the sulfur atom, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the W may be an aryl groupsubstituted with at least one halogen atom. In the above, the W may bean aryl group, substituted with at least one halogen atom, for example,an aryl group that has 6 to 12 carbon atoms and that is substituted with2 or more, 3 or more, 4 or more, or 5 or more halogen atoms.

The 2B block may be, for example, represented by the Formula 9 below.

In Formula 9, the X₂ may be the single bond, the oxygen atom, the sulfuratom, —S(═O)₂—, the alkylene group, the alkenylene group, the alkynylenegroup, —C(═O)—X₁— or —X₁—C(═O)—, in which the X₁ is the single bond, theoxygen atom, the sulfur atom, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the R₁ to R₅ may be eachindependently hydrogen, an alkyl group, a haloalkyl group or a halogenatom. The number of the halogen atom included in the R₁ to R₅ is 1 ormore.

In Formula 9, in another embodiment, the X₂ may be the single bond, theoxygen atom, the alkylene group, —C(═O)—O— or —O—C(═O)—.

In Formula 9, the R₁ to R₅ may be each independently hydrogen, an alkylgroup, a haloalkyl group or a halogen atom, and the R₁ to R₅ may include1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atom(s)such as fluorine atom(s). The number of the halogen atom(s) such as thefluorine atom(s) included in the R₁ to R₅ may be, for example, 10 orless, 9 or less, 8 or less, 7 or less, 6 or less.

In one embodiment, the second block may be a block represented byFormula 10. Such a block used herein may be referred to as a 2C block.

In Formula 10, the T and K may be each independently the oxygen atom orthe single bond, and the U may be the alkylene group.

In one embodiment, in the 2C block, the U of Formula 10 may be thealkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8 or 1 to 4 carbonatom(s).

In another embodiment, the 2C block may be a block of the Formula 10, inwhich one of the T and K of the Formula 10 is the single bond, and theother of the T and K of the Formula 10 is the oxygen atom. In the aboveblock, the U may be the alkylene group having 1 to 20, 1 to 16, 1 to 12,1 to 8 or 1 to 4 carbon atom(s).

In still another embodiment, the 2C block may be a block of the Formula10, in which both of the T and K of the Formula 10 are the oxygen atoms.In the above block, the U may be the alkylene group having 1 to 20, 1 to16, 1 to 12, 1 to 8 or 1 to 4 carbon atom(s).

In still another embodiment, the second block may be a block includingat least one metal atom or metalloid atom. Such a block may be referredto as a 2D block. This block may improve etching selectivity when anetching process is performed with respect to, for example, a filmincluding a self-assembled block copolymer.

The metal atom or metalloid atom in the 2D block may be a silicon atom,an iron atom or a boron atom, but is not particularly limited as long asit may exhibit suitable etching selectivity due to a difference withanother atom in the block copolymer.

The 2D block may include 1 or more, 2 or more, 3 or more, 4 or more, or5 or more halogen atoms, for example, fluorine atoms, along with themetal or metalloid atom. The 2D block may include 10 or less, 9 or less,8 or less, 7 or less, or 6 or less halogen atoms such as fluorine atoms.

The 2D block may be represented by Formula 11.

In Formula 11, the B may be a monovalent substituent having an aromaticstructure including a halogen atom and a substituent having the metalatom or the metalloid atom.

The aromatic structure of Formula 11 may be an aromatic structure having6 to 12 carbon atoms, for example, an aryl group or an arylene group.

The 2D block of the Formula 11 may be represented by the Formula 12below.

In Formula 12, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ is thehydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ is the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the W may be an aryl groupincluding at least one halogen atom and a substituent including themetal atom or the metalloid atom.

In the above, the W may be an aryl group that has 6 to 12 carbon atomsand that includes at least one halogen atom and a substituent includingthe metal atom or the metalloid atom.

The aryl group may include at least one or 1 to 3 substituents includingthe metal atom or metalloid atom, and 1 or more, 2 or more, 3 or more, 4or more, or 5 or more halogen atom(s).

10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atomsmay be included therein.

The 2D block of the Formula 12 may be represented by the Formula 13below.

In Formula 13, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ may bethe hydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ may be the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, the R₁ to R₅ may be eachindependently the hydrogen, the alkyl group, the haloalkyl group, thehalogen atom or the substituent including the metal or the metalloidatom, with the provision that at least one of R₁ to R₅ includes ahalogen atom, and at least one of R₁ to R₅ is the substituent includingthe metal or the metalloid atom.

In the Formula 13, 1 or more, 1 to 3 or 1 to 2 of the R₁ to R₅ may bethe substituent including the metal or the metalloid atom.

In the Formula 13, in the R₁ to R₅, 1 or more, 2 or more, 3 or more, 4or more or 5 or more halogen atom(s) may be included. The number of thehalogen atom(s) included in the R₁ to R₅ may by 10 or less, 9 or less, 8or less, 7 or less, or 6 or less.

The substituent including the metal or the metalloid atom describedabove may be carboranyl group or silsesquioxanyl group such aspolyhedral oligomeric silsesquioxanyl, ferrocenyl group ortrialkylsiloxy group. However, they are not particularly limited, aslong as they are selected so as to obtain the etching selectivity byincluding at least one metal or metalloid atom.

In yet another embodiment, the second block may be a block including anatom which is an atom having the electronegativity of 3 or more andwhich is an atom (hereinafter, referred to as a non-halogenic atom) thatis not the halogen atom. Such a block may be referred to as a 2E block.In another embodiment, the electronegativity of the non-halogenic atomin the 2E block may be 3.7 or less.

The non-halogenic atom in the 2E block may be, but is not limited to, anitrogen atom or an oxygen atom.

The 2E block may include, along with the non-halogenic atom having anelectronegativity of 3 or more, 1 or more, 2 or more, 3 or more, 4 ormore, or 5 or more halogen atoms, for example, fluorine atoms. Thenumber of the halogen atom(s) such as the fluorine atom(s) in the 2Eblock may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 orless.

The 2E block may be represented by Formula 14.

In Formula 14, the B may be a monovalent substituent having an aromaticstructure that includes a substituent including the non-halogenic atomhaving an electronegativity of 3 or more and that includes the halogenatom.

The aromatic structure of Formula 14 may be an aromatic structure having6 to 12 carbon atoms, for example, an aryl group or an arylene group.

In another embodiment, the block of the Formula 14 may be represented bythe Formula 15 below.

In Formula 15, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ may bethe hydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ may be the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the W may be the arylgroup including the substituent including the non-halogenic atom havingan electronegativity of 3 or more and at least one halogen atom.

In the above, the W may be an aryl group that has 6 to 12 carbon atoms,that includes the substituent including the non-halogenic atom havingthe electronegativity of 3 or more and that includes at least onehalogen atom.

Such an aryl group may include at least one or 1 to 3 substituentsincluding the non-halogenic atom having the electronegativity of 3 ormore. In addition, the aryl group may include 1 or more, 2 or more, 3 ormore, 4 or more, or 5 or more halogen atom(s). In the above, the arylgroup may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 orless halogen atoms.

In another embodiment, the block of the Formula 15 may be represented bythe Formula 16.

In Formula 16, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ may behydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ may be the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the R₁ to R₅ may be eachindependently hydrogen, the alkyl group, the haloalkyl group, thehalogen atom and the substituent including the non-halogenic atom havingthe electronegativity of 3 or more. In the above, at least one of the R₁to R₅ is the halogen atom, and at least one of the R₁ to R₅ is thesubstituent including the non-halogenic atom having theelectronegativity of 3 or more.

In Formula 16, at least one, 1 to 3, or 1 to 2 of the R₁ to R₅ may bethe above-described substituents including the non-halogenic atom havingthe electronegativity of 3 or more.

In Formula 16, the R₁ to R₅ may include 1 or more, 2 or more, 3 or more,4 or more, or 5 or more halogen atoms. The R₁ to R₅ may include 10 orless, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

The substituent including the non-halogenic atom having theelectronegativity of 3 or more described above may be, but is notlimited to, the hydroxyl group, the alkoxy group, the carboxyl group,the amido group, the ethylene oxide group, the nitrile group, thepyridine group or the amino group.

In another embodiment, the second block may include an aromaticstructure having a heterocyclic substituent. Such a second block may bereferred to as a 2F block herein.

The 2F block may be represented by Formula 17.

In Formula 17, the B may be a monovalent substituent having an aromaticstructure that has 6 to 12 carbon atoms and that is substituted with aheterocyclic substituent.

If necessary, the aromatic structure of Formula 17 may include at leastone halogen atom.

The block of the Formula 17 may be represented by the Formula 18.

In Formula 18, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ may behydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ may be the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the W may be an aryl groupthat has 6 to 12 carbon atoms and that has the heterocyclic substituent.

The block of the Formula 18 may be represented by Formula 19.

In Formula 19, the X₂ may be the single bond, the oxygen atom, thesulfur atom, —NR₁—, —S(═O)₂—, the alkylene group, the alkenylene group,the alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, in which the R₁ may behydrogen, the alkyl group, the alkenyl group, the alkynyl group, thealkoxy group or the aryl group, and the X₁ may be the single bond, theoxygen atom, the sulfur atom, —NR₂—, —S(═O)₂—, the alkylene group, thealkenylene group or the alkynylene group, and the R₁ to R₅ may be eachindependently hydrogen, the alkyl group, the haloalkyl group, thehalogen atom or the heterocyclic substituent. In the above, at least oneof the R₁ to R₅ is the heterocyclic substituent.

In Formula 19, at least one, for example, 1 to 3 or 1 to 2 of the R₁ toR₅ may be the heterocyclic substituent, and the other(s) may be thehydrogen atom, the alkyl group or the halogen atom; or the hydrogen atomor the halogen atom; or the hydrogen atom.

The above-described heterocyclic substituent may be, but is not limitedto, a substituent derived from phthalimide, a substituent derived fromthiopene, a substituent derived from thiazole, a substituent derivedfrom carbazole or a substituent derived from imidazole.

The block copolymer of the present application may include at least oneof the above-described first blocks, and at least one of theabove-described second blocks. Such a block copolymer may include 2 or 3blocks, or 3 or more blocks. In one embodiment, the block copolymer maybe a diblock copolymer including any one of the first blocks and any oneof the second blocks.

The block copolymer may have, for example, a number average molecularweight (Mn) in a range from approximately 3,000 to 300,000. The term“number average molecular weight” as used herein may refer to aconverted value with respect to the standard polystyrene measured by theGPC (Gel Permeation Chromatography). Unless defined otherwise, the term“molecular weight” as used herein may refer to the number averagemolecular weight. The molecular weight (Mn), in another embodiment, maybe, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more,11000 or more, 13000 or more or 15000 or more. The molecular weight(Mn), in another embodiment, may be, for example, 250000 or less, 200000or less, 180000 or less, 160000 or less, 140000 or less, 120000 or less,100000 or less, 90000 or less, 80000 or less, 70000 or less, 60000 orless, 50000 or less, 40000 or less, 30000 or less, or 25000 or less. Theblock copolymer may have the polydispersity (Mw/Mn) in a range from 1.01to 1.60. In another embodiment, the polydispersity may be about 1.1 ormore, about 1.2 or more, about 1.3 or more, or about 1.4 or more.

In the above range, the block copolymer may exhibit an appropriate selfassembling property. The number average molecular weight and the like ofthe block copolymer may be controlled considering the objected selfassembled structure.

If the block copolymer at least includes the first and second blocks, aratio of the first block, for example, the block including the chain inthe block copolymer may be in a range of 10 mole % to 90 mole %.

The present application relates to a polymer layer including the blockcopolymer. The polymer layer may be used in various applications. Forexample, it can be used in a biosensor, a recording media such as aflash memory, a magnetic storage media or the pattern forming method oran electric device or an electronic device, and the like.

In one embodiment, the block copolymer in the polymer layer may beforming a periodic structure including a sphere, a cylinder, a gyroid,or a lamella by the self assembly.

For example, in the block copolymer, one segment may be forming theregular structure such as lamella form, cylinder form and the like inthe other segment formed by the first block, the second block or otherblock linked to the first or second block via a covalent bond.

The present application relates also to a method for forming a polymerlayer by using the block copolymer. The method may include forming apolymer layer including the block copolymer on a substrate in aself-assembled state. For example, the method may include forming alayer of the block copolymer or a coating solution in which the blockcopolymer is diluted in suitable solvent on the substrate by a coatingand the like, and if necessary, then aging or heat-treating the layer.

The aging or the heat treatment may be performed based on, for example,a phase transition temperature or glass transition temperature of theblock copolymer, and for example, may be performed at a temperaturehigher than the glass transition temperature or phase transitiontemperature. A time for the heat treatment is not particularly limited,and the heat treatment may be performed for approximately 1 minute to 72hours, but may be changed if necessary. In addition, the temperature ofthe heat treatment of the polymer layer may be, for example, 100° C. to250° C., but may be changed in consideration of the block copolymer usedherein.

The formed layer may be aged in a non-polar solvent and/or a polarsolvent at the room temperature for approximately 1 minute to 72 hours.

The present application relates also to a pattern-forming method. Themethod may include selectively removing the first or second block of theblock copolymer from a laminate comprising a substrate and a polymerlayer that is formed on a surface of the substrate and that includes aself-assembled block copolymer. The method may be a method for forming apattern on the above substrate. For example, the method may includeforming the polymer layer on the substrate, selectively removing oneblock or two or more blocks of the block copolymer that is in thepolymer layer; and then etching the substrate. By the above method, forexample, nano-scaled micropattern may be formed. Further, according toshapes of the block copolymer in the polymer layer, various shapes ofpattern such as nano-rod or nano-hole can be formed by the above method.If necessary, in order to form a pattern, the block copolymer may bemixed with another copolymer or homopolymer. A kind of the substrateapplied to this method may be selected without particular limitation,and, for example, silicon oxide and the like may be applied.

For example, according to the method, a nano-scale pattern of siliconoxide having a high aspect ratio may be formed. For example, varioustypes of patterns such as a nanorod or nanohole pattern may be formed byforming the polymer layer on the silicon oxide, selectively removing anyone block of the block copolymer in a state where the block copolymer inthe polymer layer is formed in a predetermined structure, and etchingthe silicon oxide in various methods, for example, reactive ion etching.In addition, according to the above method, a nano pattern having a highaspect ratio can be formed.

For example, the pattern may be formed to a scale of several tens ofnanometers, and such a pattern may be applied in various uses includinga next-generation information electronic magnetic recording medium.

For example, a pattern in which nano structures, for example, nanowires,having a width of approximately 3 to 40 nm are disposed at an intervalof approximately 6 to 80 nm may be formed by the above-described method.In another embodiment, a structure in which nanoholes having a width,for example, a diameter of approximately 3 to 40 nm are disposed at aninterval of approximately 6 to 80 nm can be implemented.

In addition, in this structure, nanowires or nanoholes may be formed tohave a high aspect ratio.

In this method, a method of selectively removing any one block of theblock copolymer is not particularly limited, and for example, a methodof removing a relatively soft block by irradiating a suitableelectromagnetic wave, for example, ultra violet rays to a polymer layermay be used. In this case, conditions for ultra violet radiation may bedetermined according to a type of the block of the block copolymer, andultra violet rays having a wavelength of approximately 254 nm may beirradiated for 1 to 60 minutes.

In addition, followed by the ultra violet radiation, the polymer layermay be treated with an acid to further remove a segment degraded by theultra violet rays.

In addition, the etching of the substrate using the polymer layer fromwhich a block is selectively removed may be performed by reactive ionetching using CF₄/Ar ions, and followed by the above process, andremoving the polymer layer from the substrate by oxygen plasma treatmentmay be further performed.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 shows a SEM image of a polymer layer.

FIG. 2 shows an etching selectivity.

EFFECTS

The present application may provide the block copolymers and theirapplication. The block copolymer has an excellent self assemblingproperty and phase separation and various required functions can befreely imparted thereto as necessary.

Illustrative Embodiments

Hereinafter, the present application will be described in detail withreference to Examples and Comparative Examples, but the scope of thepresent application is not limited to the following examples.

1. NMR Analysis

The NMR analysis was performed at the room temperature by using a NMRspectrometer including a Varian Unity Inova (500 MHz) spectrometerhaving a triple resonance 5 mm probe. A sample to be analyzed was usedafter diluting it in solvent (CDCl₃) for the NMR analysis to aconcentration of approximately 10 mg/ml and a chemical shift (δ) wasexpressed in ppm.

<Abbreviation>

br=wide signal, s=singlet, d=doublet, dd=double doublet, t=triplet,dt=double triplet, q=quadruplet, p=quintuplet, m=multiplet

2. GPC(Gel Permeation Chromatograph)

The number average molecular weight and the polydispersity were measuredby the GPC (Gel Permeation Chromatograph). In a 5 mL vial, a blockcopolymer or a macroinitiator to be measured of Example or ComparativeExample and then diluted to a concentration of about 1 mg/mL. Then, thestandard sample for a calibration and a sample to be analyzed werefiltered by a syringe filter (pore size: 0.45 μm) and then analyzed.ChemStation from the Agilent technologies, Co. was used as an analysisprogram. The number average molecular weight (Mn) and the weight averagemolecular weight (Mw) were obtained by comparing an elution time of thesample with a calibration curve and then the polydispersity (PDI) wasobtained from their ratio (Mw/Mn). The measuring condition of the GPCwas as below.

<GPC Measuring Condition>

Device: a 1200 series from Agilent technologies, Co.

Column: two of PLgel mixed B from Polymer laboratories, Co. were used

Solvent: THF

Temperature of the column: 35° C.

Concentration of Sample: 1 mg/mL, 200 L injection

Standard Sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400,7200, 3940, 485)

PREPARATION EXAMPLE 1

A compound (DPM-C12) of the Formula A below was synthesized by the belowmethod. To a 250 mL flask, hydroquinone (10.0 g, 94.2 mmole) and1-bromododecane (23.5 g, 94.2 mmole) were added and dissolved in 100 mLacetonitrile, an excessive amount of potassium carbonate was addedthereto and then the mixture was reacted at 75° C. for approximately 48hours under nitrogen. After the reaction, remaining potassium carbonateand acetonitrile used for the reaction were removed. The work up wasperformed by adding a mixed solvent of dichloromethane (DCM) and water,and separated organic layers were collected and dehydrated throughMgSO₄. Subsequently, a white solid intermediate was obtained with ayield of approximately 37% using DCM through column chromatography.

<NMR Analysis Result of the Intermediate>

¹H-NMR(CDCl₃): δ6.77(dd, 4H); δ4.45(s, 1H); δ3.89(t, 2H); δ1.75(p, 2H);δ1.43(p, 2H); δ1.33-1.26(m, 16H); δ0.88(t, 3H)

The synthesized intermediate (9.8 g, 35.2 mmole), methacrylic acid (6.0g, 69.7 mmole), dicyclohexylcarbodiimide (DCC; 10.8 g, 52.3 mmole) andp-dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) were put into a flask,120 ml of methylenechloride was added, and a reaction was performed atthe room temperature for 24 hours under nitrogen. After the reaction wascompleted, a urea salt produced in the reaction was removed through afilter, and remaining methylenechloride was also removed. Impuritieswere removed using hexane and DCM (dichloromethane) as mobile phasesthough column chromatography, and the obtained product wasrecrystallized in a mixed solvent of methanol and water (mixed in 1:1weight ratio), thereby obtaining a white solid product (DPM-C12)(7.7 g,22.2 mmol) with a yield of 63%.

<NMR analysis result with respect to DPM-C12>

¹H-NMR(CDCl₃): δ7.02(dd, 2H); δ6.89(dd, 2H); δ6.32(dt, 1H); δ5.73(dt,1H); δ3.94(1, 2H); δ2.05(dd, 3H); δ1.76(p, 2H); δ1.43(p, 2H);1.34-1.27(m, 16H); δ0.88(1, 3H)

In the above, the R is a linear alkyl having 12 carbon atoms.

EXAMPLE 1

Synthesis of a Monomer

The compound of the Formula I below was synthesized according to thebelow method. Pentafluorostyrene (25 g, 129 mmole) was added to a mixedsolution of 400 mL of tert-butanol and potassium hydroxide (37.5 g, 161mmole); and then was subjected to a reflux reaction for 2 hours. Theproduct after the reaction was cooled to the room temperature, 1200 mLof water was added and the remaining butanol used for the reaction wasvolatilized. The adduct was extracted 3 times by diethyl ether (300 mL),an aqueous layer was acidified by 10 weight % of hydrochloric acidsolution until its pH became 3, and thereby target product wasprecipitated. Precipitated product was extracted 3 times by diethylether (300 mL) and an organic layer was collected. The organic layer wasdehydrated by MgSO₄ and solvent was removed. Crude product was purifiedin a column chromatograph by using hexane and DCM (dichloromethane) asmobile phase and thereby a colorless liquid intermediate(3-hydroxy-1,2,4,5-tetrafluorostyrene) (11.4 g) was obtained. Its NMRanalysis result is as below.

<NMR Analysis Result>

¹H-NMR(DMSO-d): δ11.7 (s, 1H); δ6.60(dd, 1H); δ5.89(d, 1H); δ5.62(d, 1H)

The intermediate (11.4 g, 59 mmole) was dissolved in DCM(dichloromethane) (250 mL) and then imidazole (8.0 g, 118 mmole), DMPA(p-dimethylaminopyridine (0.29 g, 2.4 mmole) andtert-butylchlorodimethylsilane (17.8 g, 118 mmole) were added thereto.The mixture was reacted by stirring it at the room temperature for 24hours and the reaction was terminated by adding 100 mL of brine and thenadditional extraction was performed by DCM. A collected organic layer ofDCM was dehydrated by MgSO₄ and solvent was removed so as to obtaincrude product. Colorless liquid target product (10.5 g) was obtainedafter purification in a column chromatograph by using hexane and DCM asmobile phase. NMR result of the target product is as below.

<NMR Analysis Result>

¹H-NMR(CDCl₃): δ6.62(dd, 1H); δ6.01(d, 1H); δ5.59(d, 1H); δ1.02(1, 9H),δ0.23(1, 6H)

Synthesis of a Block Copolymer

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible additionfragmentation chain transfer) reagent (2-cyano-2-propyl dodecyltrithiocarbonate) and the compound (DPM-C12) of Preparation Example 1were dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT reagent:AIBN)(Concentration: 70 weight %), and then a macroinitiator (a numberaverage molecular weight: 14000, polydispersity: 1.2) was prepared byreacting the mixture for 4 hours at 70° C. under nitrogen. Then, inbenzene, the synthesized macroinitiator, the compound (TFS-S) of FormulaI and AIBN (azobisisobutyronitrile) were dissolved in a weight ratio of1:200:0.5 (the macroinitiator:TFS-S:AIBN) (Concentration: 30 weight %),and then a block copolymer (a number average molecular weight: 35000,polydispersity: 1.2) was prepared by reacting the mixture for 6 hours at70° C. under nitrogen. The block copolymer includes the first blockderived from the compound of Preparation Example 1 and the second blockderived from the compound of Formula I.

COMPARATIVE EXAMPLE 1

2.0 g of the compound (DPM-C12) of Preparation Example 1, 64 mg of RAFT(Reversible Addition-Fragmentation chain transfer) reagent(cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile)and 5.34 mL of benzene were added to a 10 mL flask and then were stirredat the room temperature for 30 minutes and then the RAFT (reversibleaddition fragmentation chain transfer) polymerization was performed at70° C. for 4 hours. After the polymerization, the reacted solution wasprecipitated in 250 mL of methanol that was an extraction solvent, wasvacuum filtered and dried so as to obtain pink macroinitiator. The yieldof the macroinitiator was about 86%, and its number average molecularweight (Mn) and polydispersity (Mw/Mn) were 9,000 and 1.16,respectively.

0.3 g of the macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mLof benzene were added to a 10 mL Schlenk flask and then were stirred atthe room temperature for 30 minutes and then the RAFT (reversibleaddition fragmentation chain transfer) polymerization was performed at115° C. for 4 hours. After the polymerization, the reacted solution wasprecipitated in 250 mL of methanol that was an extraction solvent, wasvacuum filtered and dried so as to obtain light pink block copolymer.The yield of the block copolymer was about 18%, and its number averagemolecular weight (Mn) and polydispersity (Mw/Mn) were 16,300 and 1.13,respectively. The block copolymer includes the first block derived fromthe compound (DPM-C12) of Preparation Example 1 and the second blockderived from the pentafluorostyrene.

TEST EXAMPLE 1

Self assembled polymer layer was prepared by using block copolymers ofExample 1 and the result was observed. Specifically, the block copolymerwas dissolved in solvent to a concentration of 1.0 weight % and then wasspin-coated on a silicone wafer for 60 seconds by a speed of 3000 rpm.Then, self assembling was performed by a thermal annealing performed at160° C. for 1 hour. Then, the self assembling properties were evaluatedby subjecting the polymer layer to a SEM (scanning electron microscope)analysis. FIG. 1 is the results of Example 1, and from the above, it canbe confirmed that an appropriate phase separation was realized.

TEST EXAMPLE 2

Etching resistance was evaluated with respect to the block copolymer ofthe Example 1 or Comparative Example 1. Specifically, the etchingprocesses were performed under the same conditions (RF power: 150 W,pressure: 15 mTorr) with an etching device (SNTech), and etchingselectivity was compared. The result is illustrated in FIG. 2. In FIG.2, the X axis is the etching time and the Y axis is a percentage showingremaining film thickness during the etching process. In FIG. 2, the PDPMexhibits the etching time with respect to the first block of the Example1 and Comparative Example 1 and the PTFSis exhibits the etching timewith respect to the second block of the Example 1 and the PPFS exhibitsthe etching time with respect to the second block of the ComparativeExample 1. From FIG. 2, it can be confirmed that the block copolymer ofExample 1 exhibits an excellent etching selectivity, since there is abig difference between the etching resistance of the first block and theetching resistance of the second block.

What is claimed is:
 1. A block copolymer comprising a first block of the Formula 5 below and a second block comprising at least one metal atom or metalloid atom:

wherein the R is hydrogen or an alkyl group having 1 to 4 carbon atom(s), the X is a single bond, an oxygen atom, —C(═O)—O— or —O—C(═O)—, the P is an arylene group, the Q is an oxygen or or —NR₃—, where the R₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group and the Z is a linear chain having 8 or more chain-forming atoms.
 2. The block copolymer according to claim 1, wherein the linear chain comprises 8 to 20 chain-forming atoms.
 3. The block copolymer according to claim 1, wherein the chain-forming atom is carbon, oxygen, nitrogen or sulfur.
 4. The block copolymer according to claim 1, wherein the chain-forming atom is carbon or oxygen.
 5. The block copolymer according to claim 1, wherein the linear chain is a hydrocarbon chain.
 6. The block copolymer according to claim 1, wherein the metal atom or metalloid atom is silicon, iron or boron.
 7. The block copolymer according to claim 1, wherein the second block further comprises halogen.
 8. The block copolymer according to claim 7, the halogen is fluorine.
 9. The block copolymer according to claim 1, wherein the second block is represented by the Formula 11 below:

wherein the B is a monovalent substituent having an aromatic strucutre comprsing halogen atom and a substituent comprising the metal or metalloid atom.
 10. The block copolymer according to claim 9, wherein the B of the Formula 11 is a monovalent substituent having an aromatic strucutre which has 6 to 12 carbon atoms and which comprises at least 3 halogen atoms and a substituent comprising the metal or metalloid atom.
 11. The block copolymer according to claim 1, wherein the second block is represented by the Formula 13 below:

wherein the X₂ is a single bond, oxygen atom, sulfur atom, —NR₁—, —S(═O)₂—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X₁— or —X₁—C(═O)—, where the R₁ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and the X₁ is a single bond, oxygen atom, sulfur atom, —NR₂—, —S(═O)₂—, an alkylene group, an alkenylene group or an alkynylene group, the R₁ to R₅ are each independently hydrogen, an alkyl group, a haloalkyl group, an halogen atom or a substituent including the metal or the metalloid atom, with the provision that at least one of the R₁ to R₅ comprises a halogen atom, and at least one of the R₁ to R₅ is the substituent including the metal or the metalloid atom.
 12. The block copolymer according to claim 1, wherein the metal or metalloid atom is comprised in carboranyl group or silsesquioxanyl, ferrocenyl group or trialkylsiloxy group.
 13. A polymer layer comprising a self assembled product of the block copolymer of claim
 1. 14. A method for forming a polymer layer, comprising forming the polymer layer comprising a self assembled product of the block copolymer of claim
 1. 15. A pattern-forming method comprising selectively removing the first or second block of the block copolymer from a laminate comprising a substrate and a polymer layer that is formed on the substrate and that comprises a self-assembled product of the block copolymer of claim
 1. 